JP2015506821A - Heavy oil catalytic cracking catalyst and method for producing the same - Google Patents

Abstract

The present invention comprises 2 to 50% by weight of ultrastable rare earth Y-type molecular sieve, 0.5 to 30% by weight of one or more other molecular sieves, 0.5 to 70% by weight of clay, and 1.0 to The present invention relates to a heavy oil catalytic cracking catalyst containing 65% by weight and 0.01 to 12.5% by weight of rare earth oxide and a method for producing the same. The ultra-stable rare earth Y-type molecular sieve is made of NaY molecular sieve as a raw material, and after passing through rare-earth exchange and dispersion pre-exchange that may not be limited sequentially, the molecular sieve slurry is further filtered, washed with water and fired for the first time, "One exchange and one calcination" rare earth sodium Y molecular sieve is obtained, "One exchange and one calcination" rare earth sodium Y molecular sieve is reduced with sodium by ammonium salt exchange, and second firing is performed to obtain an ultrastable rare earth Y molecular sieve It is done. The catalyst provided in the present invention is characterized by a strong heavy oil conversion ability and high liquid total yield and light oil yield.

Description

  The present invention relates to a heavy oil catalytic cracking catalyst exhibiting high heavy oil conversion ability and a method for producing the same. More specifically, the present invention relates to a catalytic cracking catalyst applied to kneaded residue oil and a method for producing the catalyst.

  Catalytic cracking equipment is an important secondary processing means of crude oil, and the distribution of the total product thereby determines the economics of the refinery. In recent years, as the tendency of raw material oils to become heavier and lower has progressed, FCC catalysts require stronger heavy oil conversion ability and selectivity of high-value products. As the main provider of cracking activity of heavy oil cracking catalysts, Y-type molecular sieves are the factors that determine the heavy oil conversion capacity of FCC catalysts because of their superiority and inferior activity stability and cracking activity.

  Therefore, many related research organizations in Japan and overseas are studying how to improve the degradation activity and activity stability of Y-type molecular sieves. Currently, in the process of modification of molecular sieves with rare earths, rare earth ions are localized in the sodalite cage as much as possible to suppress dealumination of the molecular sieve skeleton in the process of water vapor degradation, thereby stabilizing the structural stability and activity of the molecular sieve skeleton. It is thought to improve the performance. In Chinese patent ZL200410058089.3, a method for producing a rare earth-modified Y-type molecular sieve is disclosed. After the rare earth exchange reaction is completed, the method is adjusted to pH 8 to 11 using an alkaline solution, and then the usual method is used. Subsequent processing procedures are performed, and all the molecular sieve rare earth ions prepared by the method are localized in a cage (sodalite cage). In Chinese Patent ZL200410058090.6, the molecular sieve reaction performance in Chinese Patent ZL200410058089.3 is published, and according to the catalytic reaction result, the structure of molecular sieve is determined by the localization of rare earth ions in sodalite cage. Stability and activity stability are improved and the heavy oil conversion ability of the catalyst is clearly improved, but it becomes clear that the coke selectivity by the catalyst is poor.

  Chinese Patent ZL97122039.5 discloses a method for producing ultra-stable Y zeolite, in which Y-type zeolite is contacted with one acid solution and one ammonium ion-containing solution for high-temperature steam treatment. The amount of the acid used is 1.5 to 6 mole hydrogen ions per mole of skeletal aluminum, the concentration of the acid solution is 0.1 to 5 equivalents / liter, and the contact temperature between the Y-type zeolite and the acid solution is 5 to 100. C., the contact time is 0.5 to 72 hours, and the weight ratio of Y-type zeolite to ammonium ions is 2 to 20. In the modification method according to the patent, it is necessary to add an ammonium ion-containing solution. For that purpose, the content of sodium oxide in the molecular sieve is reduced or the acidic gas is destroyed to the molecular sieve structure in the firing process. The FCC catalyst prepared using the molecular sieve is characterized by strong heavy oil conversion ability and high yield of light oil, but the molecular sieve modification technology is the following technology. 1) A large amount of ammonium ions are added during the preparation process, and ammonium ions are finally introduced into the atmosphere or wastewater, resulting in increased ammonia nitrogen contamination and management costs; 2) Molecular sieves according to the patented method The problem of particle aggregation cannot be solved effectively, and The specific surface and pore volume of the molecular sieve are reduced, and the resistance of the pore passage during the molecular sieve exchange process is increased, making it difficult to accurately localize and quantify the modified elements in the molecular sieve; 3) At the same time, the patent further mentions that the Y-type zeolite may be brought into contact with the ammonium ion-containing solution, or thereafter, rare earth ions may be introduced by ion exchange, and in the exchange process, ammonium ions and rare earth ions are introduced. There is a competitive reaction between the ammonium ions and the rare earth ions preferentially occupying the sites, increasing the resistance of rare earth ions to exchange and enter the molecular sieve cage, and reducing the utilization efficiency of the rare earth ions. , Will lead to.

  In Chinese Patent ZL02103909.7, a method for producing a rare earth-containing ultrastable Y-type molecular sieve is disclosed, which is obtained by changing NaY molecular sieve once and firing once, and NaY molecular sieve. The sieve is put in an ammonium ion solution and subjected to a chemical dealumination treatment at 25 to 100 ° C. The chemical dealumination complex contains oxalic acid and / or oxalate, and the treatment time is 0.5 to 5 hours, and thereafter Then, a rare earth solution is added and stirred to produce a rare earth precipitate containing rare earth oxalate, filtered, washed with water to form a cake, and further subjected to hydrothermal treatment to produce a molecular sieve product. The molecular sieve prepared by this method has a certain resistance to fouling by vanadium, but its activity stability and decomposition activity are low, and it does not meet the trend of increasing the weight and quality of feedstock. This is mainly due to the position distribution of rare earth ions in the molecular sieve supercage and sodalite cage in the modification process of the molecular sieve. As clarified by the method, rare earth ions exist in the molecular sieve system in two types, that is, some rare earth ions enter the sodalite cage in ionic form and other rare earth ions are rare earth oxides. (The precursor is rare earth oxalate, which is converted to rare earth oxide by subsequent firing) and is dispersed independently on the surface of the molecular sieve, which provides a stable support of rare earth ions for the molecular sieve structure. In addition to the reduction, there are many problems of ammonia nitrogen contamination in the method, and the poisoning of oxalic acid and / or oxalate added to the environment and human body is large.

  CN200410029875.0 discloses a method for producing a rare earth ultrastable Y-type zeolite, which uses a mixed solution consisting of a rare earth salt and citric acid or a mixed solution consisting of an inorganic ammonium salt, a rare earth salt and citric acid. The process of processing is included. The process simplifies the process, and the prepared zeolite is used as an active component of the cracking catalyst to reduce the olefin content, which is the product of catalytic cracking of gasoline, and of the product of catalytic cracking of light oil. Although there is a clear advantage in increasing the yield, the method does not account for the localization of rare earth ions in the molecular sieve.

  The present invention is a novel catalytic cracking catalyst capable of converting heavy oil efficiently and having a high heavy oil conversion ability, a suitable coke selectivity, and a high yield of a target product. It aims at providing the manufacturing method.

  In the composition of the catalyst, 2 to 50% by weight of ultrastable rare earth Y-type molecular sieve, 0.5 to 30% by weight of one or more other molecular sieves, 0.5 to 70% by weight of clay, high temperature resistant inorganic Catalytic cracking catalyst of heavy oil containing 1.0 to 65% by weight of oxide and 0.01 to 12.5% by weight of rare earth oxide, ultrastable rare earth Y-type molecular sieve is prepared by a preparation process including rare earth exchange and dispersion pre-exchange. In the ultrastable rare earth Y-type molecular sieve, 0.5 to 25% by weight of rare earth oxide, 1.2% by weight or less of sodium oxide, 40 to 75% crystallinity, and 2.449 nm to 2.472 nm in lattice constant The rare earth exchange and the dispersion pre-exchange are not limited sequentially but are performed continuously, and there is no firing process between them; the dispersion pre-exchange is performed by adjusting the concentration of the molecular sieve slurry to 80 to 400 g / L as the solid content. , 0.2% to 7% by weight of dispersant The dispersion preliminary exchange is performed, the exchange temperature is 0 to 100 ° C., the exchange time is 0.1 to 1.5 hours; the above dispersants in the dispersion preliminary exchange are sesbania powder, boric acid, urea, ethanol, polyacrylamide , Acetic acid, oxalic acid, adipic acid, formic acid, hydrochloric acid, nitric acid, citric acid, salicylic acid, tartaric acid, benzoic acid, one or more selected from starch; A novel catalytic cracking catalyst capable of converting heavy oil efficiently, which is characterized in that it is not used.

  The present invention further provides the following method for producing the heavy oil catalytic cracking catalyst.

(1) Preparation of ultra-stable rare earth Y-type molecular sieve: NaY molecular sieve (preferably having a caivan ratio of greater than 4.0 and a crystallinity of greater than 70%) is used as a raw material. Through the exchange, the molecular sieve slurry is further filtered, washed with water and fired for the first time to obtain a “one exchange and one firing” rare earth sodium Y molecular sieve, and the order of rare earth exchange and dispersion pre-exchange is not limited, “One-exchange-one-fired” rare earth sodium Y molecular sieve is reduced by sodium exchange by ammonium salt exchange, and then fired a second time to obtain an ultra-stable rare-earth Y-type molecular sieve.
(2) Preparation of heavy oil catalyst: Mixing and homogenizing the above-mentioned molecular sieve component, which is an ultrastable rare earth Y-type, and a precursor of clay and high temperature resistant inorganic oxide, spray molding, firing and washing with water to complete the catalyst Goods are obtained.

In step (1) in the process of preparing the heavy oil catalytic cracking catalyst described in the present invention, that is, when an ultrastable rare earth Y-type molecular sieve is obtained, the molecular sieves are exchanged between the NaY molecular sieve rare earth exchange and the dispersion pre-exchange. The rally may not be washed and filtered, and may be washed and filtered. During the rare earth exchange, the RE ₂ O ₃ / Y zeolite (mass) is preferably 0.005 to 0.25, most preferably 0.01 to 0.20, the exchange temperature is 0 to 100 ° C, and 60 to 95 ° C is the most. Preferably, the exchange pH value is 2.5 to 6.0, most preferably 3.5 to 5.5, the exchange time is 0.1 to 2 hours, and most preferably 0.3 to 1.5 hours. In the dispersion pre-exchange, the amount of the dispersant added is 0.2 wt% to 7 wt%, most preferably 0.2 wt% to 5 wt%, the exchange temperature is 0 to 100 ° C., and 60 to 95 ° C. is the most. Preferably, the exchange time is 0.1 to 1.5 hours. The modified molecular sieve slurry is filtered and washed with water to obtain a cake. The obtained cake is flash-dried so that the water content is 30% to 50%, and the final baking is performed. Ordinary conditions may be used. For example, baking may be performed at 350 ° C. to 700 ° C. with 0 to 100% steam for 0.3 to 3.5 hours, and 450 ° C. to 650 ° C. with 15 to 100% steam for 0.5 to 2.5 hours. Preferably, this results in a “one exchange one calcined” ultrastable rare earth sodium Y molecular sieve. "1 exchange 1 firing" ultrastable rare earth sodium Y molecular sieve is obtained through the second exchange and the second firing to obtain the ultrastable rare earth Y type molecular sieve described in the present invention, the second exchange, the second firing Is a process of sodium reduction and ultrastabilization by ammonium salt exchange well known in the industry, and is not particularly limited in the present invention.

  In the “one-exchange-one-firing” process of the ultrastable rare earth Y-type molecular sieve described in the present invention, pot-type exchange, belt-type exchange, and / or cake exchange may be employed in the exchange process of rare earth exchange and dispersion pre-exchange. . When performing rare earth exchange, it may be performed as follows, that is, assuming that the total amount of rare earth does not change, the rare earth compound solution is divided into multiple parts, pot type exchange, belt type exchange and / or cake exchange That is, a plurality of exchanges may be performed. Similarly, in the dispersion pre-exchange process, it is also possible to divide the dispersant into a plurality of parts and perform pot type exchange, belt type exchange and / or cake exchange on the assumption that the total amount of the dispersant does not change. When the rare earth exchange and the dispersion pre-exchange are a plurality of exchanges, the two kinds of exchanges may be performed alternately.

  The rare earth compounds described in the present invention are rare earth chloride, rare earth nitrate and rare earth sulfate, and rare earth chloride and rare earth nitrate are preferred.

  The rare earth described in the present invention may be lanthanum enriched rare earth or cerium enriched rare earth, or pure lanthanum or pure cerium.

  In the dispersion pre-exchange process described in the present invention, the dispersant is sesbania powder, boric acid, urea, ethanol, polyacrylamide, acetic acid, oxalic acid, adipic acid, formic acid, hydrochloric acid, nitric acid, citric acid, salicylic acid, tartaric acid, One or more kinds selected from benzoic acid and starch, and two or more kinds are preferred.

  Other molecular sieves in the catalyst composition described in the present invention are Y type zeolite, L zeolite, ZSM-5 zeolite, b zeolite, aluminum phosphate zeolite, one or more types selected from W zeolite, Preference is given to Y-type zeolite, ZSM-5 zeolite, b zeolite, or the usual physical or chemical modifications of the above mentioned zeolites, HY, USY, REY, REHY, REUSY, H-ZSM-5, Hb. including.

The clay described in the present invention is one or more selected from kaolin, halloysite, montmorillonite, sepiolite, pearlite, and the like, and the high-temperature resistant inorganic oxide includes Al ₂ O ₃ , SiO ₂ , SiO ₂ One or more selected from _2- Al ₂ O ₃ and AlPO ₄ , and precursors thereof include silica alumina gel, silica sol, alumina sol, silica alumina composite sol, and pseudoboehmite.

  The spraying conditions described in the present invention are the operating conditions for preparing a normal cracking catalyst, and in the present invention, there is no limitation, the post-treatment process is the same as in the prior art, including catalyst calcination, water washing, drying, etc. Above all, for firing, it is preferable that the sprayed microsphere sample is fired at 200 ° C. to 700 ° C., more preferably 300 ° C. to 650 ° C., the time is 0.05 to 4 hours, 0.1 to 3.5 hours are preferable, and the washing conditions are preferable. The water / catalyst weight is 0.5 to 35, the washing temperature is 20 ° C. to 100 ° C., and the time is 0.1 to 0.3 hours.

About specifications of raw materials used in Examples 1. NaY molecular sieve: NaY-1 (Kayban ratio 4.8, crystallinity 92%), NaY-2 (Kayban ratio 4.1, crystallinity 83%), manufactured by Lanzhou Petrochemical Co., Ltd. Catalyst Factory.
2. Ultra-stable 1 exchange 1 calcined molecular sieve sample: 60% crystallinity, 4.3m% sodium oxide, manufactured by Lanzhou Petrochemical Company.
3. Rare earth solution: rare earth chloride (rare earth oxide 277.5g / l), rare earth nitrate (rare earth oxide) 252g / l), both industrial products, obtained from Lanzhou Petrochemical's catalyst factory.
4). Sesbania powder, boric acid, urea, ethanol, polyacrylamide, oxalic acid, adipic acid, acetic acid, formic acid, hydrochloric acid, nitric acid, citric acid, salicylic acid, tartaric acid, starch are all for chemical use; ammonium chloride, ammonium nitrate, ammonium sulfate Ammonium oxalate is an industrial product.
5. Pseudo boehmite (heat loss 36.2%), kaolin (heat loss 16.4%), halloysite (heat loss 21.4%), montmorillonite (heat loss 15.8%), perlite (heat loss 17.6%) are solid Aluminum sol contains 23.0% by weight aluminum oxide; silicon sol contains 24.5% by weight silica, both of which are industrially acceptable.
6). REY, REHY, USY, and REUSY molecular sieve are all acceptable industrial products, manufactured by Lanzhou Petrochemical Co., Ltd .; b Zeolite is an industrially acceptable product, manufactured by Fushunishi Chemical; H-ZSM-5, Made by Shanghai Fudan University.

[Example 1]
In a reaction vessel with a heating jacket, add 3000 g of NaY-1 molecular sieve (anhydrous base) and a certain amount of deionized water in order to prepare a slurry with a solid content of 220 g / L, and add 82 g of boric acid and 105 g of sesbania powder. Thereafter, the temperature was raised to 85 ° C. and exchange reaction was performed for 0.5 hours with stirring, followed by filtration and washing.The resulting cake was placed in a reaction vessel, and then 1.67 liters of rare earth chloride was added, and the system pH = 4.0. To 80 ° C. and exchange reaction for 0.3 hours, the cake obtained is flash-dried so that its water content is 30% to 50%, finally 70% steam, By calcining at 670 ° C. for 1.0 hour, “one exchange and one calcined” rare earth sodium Y was obtained. To a reaction vessel with a heating jacket, add 500g (1 basis 1 calcined) ultrastable rare earth sodium Y molecular sieve (anhydrous base) and a certain amount of deionized water to prepare a slurry with a solid content of 120g / L. To adjust the pH in the system to 4.2, heated to 90 ° C., exchanged for 0.8 hours, filtered and washed, the cake was baked at 80% steam, 560 ° C. for 2.5 hours, the present invention The rare earth ultra-stable Y molecular sieve active ingredient described in 1 is prepared and denoted as modified molecular sieve A-1.

  In a reaction bath with water bath heating, 4.381 liters of water, 1062 g of kaolin, 986 g of aluminum oxide and 63.5 ml of hydrochloric acid were added and mixed uniformly. After stirring for 1 hour, 448 g of modified molecular sieve A-1 and H-ZSM-5 63 g and REUSY 755 g were added in order, and after mixing uniformly, 1500 g of aluminum sol was gradually added to gel, followed by spray molding, and the resulting microspheres were fired at 400 ° C. for 0.5 hour. Take 2 kg of the calcined microspheres, add 15 kg of deionized water, wash at 60 ° C. for 15 minutes, filter and dry to obtain the cracking catalyst prepared in the present invention, denoted as A.

[Example 2]
In a reaction vessel with a heating jacket, add 3000 g of NaY-1 molecular sieve (anhydrous base) and a certain amount of deionized water in order to prepare a slurry with a solid content of 360 g / L, add 0.82 liter of rare earth nitrate, After adjusting to pH = 3.3, raising the temperature to 80 ° C. and allowing the reaction to exchange for 1.5 hours, filtering and washing, the resulting cake was put into a reaction vessel, and further, 202 g of polyacrylamide and 30 g of salicylic acid were added. The dispersion was exchanged by raising the temperature to 78 ° C., and the exchange reaction was carried out for 0.5 hours with stirring. The cake cake obtained was rush dried so that its water content was 30% to 50%, and finally Baking for 30 hours at 30% steam and 630 ° C. for 1.8 hours produced “one-exchange-one-fired” rare earth sodium Y. In a reactor equipped with a heating jacket, put 500g (anhydrous base) of ultra-stable rare earth sodium Y molecular sieve and deionized water, and adjust the slurry to a solid content of 370g / L, and add 200g of ammonium sulfate. The system pH is adjusted to 3.6, the temperature is raised to 90 ° C., exchanged for 1.2 hours, filtered and washed, and the cake is baked at 20% steam and 600 ° C. for 0.5 hours, as described in the present invention. A rare earth ultra-stable Y molecular sieve active ingredient was prepared and denoted as modified molecular sieve B-1.

  In a reaction bath with water bath heating, 4.620 liters of water, 1024 g of kaolin, 971 g of pseudoboehmite and 90.8 ml of hydrochloric acid were added and mixed uniformly. After stirring for 1 hour, 338 g of modified molecular sieve B-1, 129 g of b zeolite, REHY 806 g was added in order, and after mixing uniformly, 1304 g of aluminum sol was gradually added to gel. After spray molding, the resulting microspheres were fired at 400 ° C. for 1.0 hour. Take 2 kg of calcined microspheres, add 20 kg of deionized water, wash at 35 ° C. for 40 minutes, filter and dry to obtain the cracking catalyst prepared in the present invention, which is denoted as B.

[Example 3]
In a reaction vessel with a heating jacket, add 3000 g of NaY-1 molecular sieve (anhydrous base) and deionized water in order to prepare a slurry with a solid content of 150 g / L, add 43 g of hydrochloric acid, and react at 85 ° C for 1 hour After that, add 1.68 liters of rare earth chloride to adjust the system pH to 3.7, raise the temperature to 90 ° C., carry out exchange reaction for 1 hour, filter the molecular sieve slurry, and change the dispersant belt type The belt-type replacement conditions are: 35 g oxalic acid is prepared so as to become a solution with a pH value of 3.4, the temperature is raised to 85 ° C., and the degree of vacuum of the belt-type filter is 0.04. The cake is flash-dried so that its moisture content is 30% to 50%, and finally baked at 10% steam and 510 ° C for 2.0 hours to obtain "1 exchange 1 baked" ultrastable rare earth sodium Y. It was made. In a reactor equipped with a heating jacket, put 500g (anhydrous base) of ultra-stable rare earth sodium Y molecular sieve and deionized water into a slurry with a solid content of 145g / L, and add 80g of ammonium sulfate. Adjust the internal pH = 3.5, raise the temperature to 90 ° C., exchange for 1.2 hours, filter, wash, baked the cake at 50% steam, 650 ° C. for 2 hours, the rare earth according to the present invention An ultrastable Y molecular sieve active ingredient was prepared and is denoted as modified molecular sieve C-1.

  Add 4.854 liters of water, 1125 g of halloysite, 825 g of pseudoboehmite and 51.4 ml of hydrochloric acid to a reaction bath with water bath heating, mix uniformly, stir for 1 hour, and then add 406 g of modified molecular sieve C-1 and 903 g of USY in order. After being uniformly mixed, 1224 g of silicon sol was gradually added to be gelled, and after spray molding, the obtained microspheres were fired at 600 ° C. for 0.3 hours. Take 2 kg of calcined microspheres, add 15 kg of deionized water, wash at 80 ° C. for 30 minutes, filter and dry to obtain the cracking catalyst prepared in the present invention, which is denoted as C.

[Example 4]
In a reaction vessel with a heating jacket, add 3000 g of NaY-1 molecular sieve (anhydrous base) and a certain amount of deionized water in order to prepare a slurry with a solid content of 320 g / L, and add 30 g of nitric acid to 85 ° C. After raising the temperature and reacting with stirring for 0.8 hours, 0.95 liters of rare earth nitrate was further added to adjust the system pH to 3.3, the temperature was raised to 80 ° C., and exchange reaction was carried out for 1.8 hours. Put 62g of starch, react at 80 ° C for 0.5 hour, react, filter and wash, flash dry the resulting cake so that its moisture content is 30% to 50%, finally A “one-exchange-one-fired” rare earth sodium Y was fired at 60% steam at 560 ° C. for 2 hours. In a reaction vessel with a heating jacket, add 500g of ultra-stable rare earth sodium Y molecular sieve (anhydrous base) and deionized water to a slurry with a solids content of 280g / L, and add 130g of ammonium sulfate. The system is adjusted to pH = 4.0, heated to 90 ° C., exchanged for 0.5 hour, filtered and washed, and the cake is baked at 60% steam at 680 ° C. for 1 hour, and is described in the present invention. A rare earth ultra-stable Y molecular sieve active ingredient was prepared and denoted as modified molecular sieve D-1.

  Add 4.577 liters of water, 1055 g of kaolin, 983 g of aluminum oxide and 63.5 ml of hydrochloric acid to a reaction bath with water bath heating, mix uniformly, and stir for 1 hour, then 892 g of modified molecular sieve D-1 and 63 g of ZSM-5 zeolite Then, 118 g of USY and 188 g of REY were added in order, and after uniform mixing, 1500 g of aluminum sol was gradually added to gel, and the resulting microspheres were fired at 400 ° C. for 0.5 hour. Take 2 kg of calcined microspheres, add 10 kg of deionized water, wash at 40 ° C. for 20 minutes, filter and dry to obtain the cracking catalyst prepared according to the present invention, denoted as D.

[Example 5]
In a reaction vessel with a heating jacket, add 3000 g of NaY-1 molecular sieve (anhydrous base) and a certain amount of deionized water in order to prepare a slurry with a solid content of 350 g / L, and add 42 g of citric acid and 28 g of sesbania powder. Then, the temperature was raised to 82 ° C., and exchange reaction was performed for 1.3 hours with stirring. After addition of 0.56 liters of rare earth nitrate and exchange reaction at 85 ° C. for 0.8 hours, the molecular sieve slurry was filtered, and the belt type The belt type replacement conditions are as follows: The temperature of the rare earth nitrate solution is raised to 88 ° C., the replacement pH value is 4.7, the rare earth nitrate addition amount is 0.04 for RE ₂ O ₃ / Y zeolite (mass), the belt The vacuum degree of the filter is 0.03, and then the cake obtained is flash dried so that its moisture content is 30% to 50%, and finally baked at 80% steam and 530 ° C for 1.5 hours Thus, “one exchange and one firing” ultrastable rare earth sodium Y is produced. In a reactor equipped with a heating jacket, add 500 g of ultra-stable rare earth sodium Y molecular sieve (anhydrous base) and deionized water to a slurry with a solid content of 150 g / L, and add 100 g of ammonium sulfate. The system pH was adjusted to 4.0, the temperature was raised to 90 ° C., exchanged for 1 hour, filtered, washed, and the cake was baked at 60% steam at 620 ° C. for 2 hours, as described in the present invention. A rare earth ultra-stable Y molecular sieve active ingredient is prepared and denoted as modified molecular sieve E-1.

  To a reaction bath with water bath heating, 6.5 liters of water, 995 g of kaolin, 676 g of aluminum oxide and 130 ml of hydrochloric acid were added and mixed uniformly. After stirring for 1 hour, 558 g of modified molecular sieve E-1 and 19 g of H-ZSM-5 Then, 830 g of REUSY was added in order, and after uniform mixing, 1359 g of aluminum sol was gradually added to form a gel. After spray molding, the obtained microspheres were fired at 500 ° C. for 0.6 hours. Take 2 kg of calcined microspheres, add 19 kg of deionized water, wash at 80 ° C. for 10 minutes, filter and dry to obtain the cracking catalyst prepared according to the present invention, denoted as E.

[Comparative Example 1]
The production method of REUSY molecular sieve is similar to the method shown in Example 3, except that hydrochloric acid and oxalic acid are not added, and other parts are the same as in Example 3, and the obtained ultrastable rare earth Y-type molecular sieve is obtained. The number of the catalyst is F-1, and the number of the obtained catalyst is F.

[Comparative Example 2]
This comparative example uses the molecular sieve manufacturing method described in CN200510114495.1, considers the reaction performance of the molecular sieve, and the catalyst manufacturing process is the same as in Example 5.

Ultra-stable 1 exchange 1 calcined molecular sieve sample produced by hydrothermal method at Lanzhou Petrochemical Co., Ltd. (1.4% Na ₂ O content, 8.6% RE ₂ O ₃ content, lattice 2.468 nm, relative crystallinity 62%), 3000 g (anhydrous basis) was taken, put into 3 liters of 2N oxalic acid aqueous solution, uniformly mixed and stirred, heated to 90-100 ° C. and reacted for 1 hour, then washed with filtered water to obtain Place the cake in 6 liters of deionized water, add 1.46 liters of rare earth nitrate solution, raise the temperature to 90-95 ° C, react for 1 hour, wash with filtered water, dry the cake at 120 ° C, compare Example A molecular sieve sample is obtained, denoted as H-1.

  To a reaction bath with water bath heating, 6.5 liters of water, 995 g of kaolin, 676 g of aluminum oxide, and 130 ml of hydrochloric acid were added and mixed uniformly. After stirring for 1 hour, modified molecular sieve H-1 558 g, H-ZSM-5 19 g Then, 830 g of REUSY was added in order, and after uniform mixing, 1359 g of aluminum sol was gradually added to form a gel. After spray molding, the obtained microspheres were fired at 500 ° C. for 0.6 hours. Take 2 kg of the calcined microspheres, add 19 kg of deionized water, wash at 80 ° C. for 10 minutes, filter and dry to obtain the cracking catalyst prepared in the present invention, denoted as H.

[Comparative Example 3]
In this comparative example, the molecular sieve manufacturing method described in CN97122039.5 is used, and the catalyst manufacturing process is the same as in Example 3.

  Add deionized water and 3000 g (anhydrous base) NaY-1 molecular sieve to a reaction vessel with a heating jacket to prepare a slurry with a solid content of 90 g / L, stir to 80 ° C, and heat up to 59 g of hydrochloric acid. Holding the constant temperature for 8 hours, adding 1.65 liters of rare earth chloride solution and 1200 g of solid ammonium chloride, stirring for 1 hour, washing with filtered water until chlorine ions are not detected, and the resulting wet cake (water content 47% ) Is calcined at 600 ° C. for 2 hours to obtain a comparative molecular sieve sample, which is denoted as G-1.

  Add 4.854 liters of water, 1125 g of halloysite, 825 g of pseudoboehmite and 51.4 ml of hydrochloric acid to a reaction bath with water bath heating, mix uniformly, stir for 1 hour, then add 406 g of modified molecular sieve G-1 and 903 g of USY in order. After uniform mixing, 1224 g of silicon sol was gradually added to gel, and after spray molding, the obtained microspheres were fired at 600 ° C. for 0.3 hours. Take 2 kg of calcined microspheres, add 15 kg of deionized water, wash at 80 ° C. for 30 minutes, filter and dry to obtain the cracking catalyst prepared in the present invention, which is denoted as G.

1. Analysis and evaluation methods used in Examples Lattice constant (a ₀ ): X-ray diffraction method.
2. Crystallinity (C / C ₀ ): X-ray diffraction method.
3. Keiban ratio: X-ray diffraction method.
4). Na ₂ O content: flame photometric method.
5. RE ₂ O ₃ content: Colorimetric method.
6). Micro Activity: Samples are pretreated for 4 hours at 800 ° C. and 100% steam conditions. The reaction raw material is Oko light diesel, the reaction temperature is 460 ° C, the reaction time is 70 seconds, the catalyst charge is 5.0g, the catalyst / oil weight ratio is 3.2, and the total conversion rate is micro reaction activity.
7). ACE heavy oil microreactor: The reaction temperature is 530 ° C, the catalyst / oil ratio is 5, and the feedstock oil is a vacuum residue oil kneaded with 30% of fresh oil.

  Table 1 shows the physicochemical properties of the ultrastable rare earth Y-type molecular sieves obtained in the inventive examples and comparative examples. As a result of analysis, the novel molecular sieve has the characteristics that the structural stability is good and the particle size is small compared to the comparative example.

  Table 2 shows the evaluation results of the reaction performance of the catalysts prepared in Examples 1 to 5 and Comparative Example.

From the results of ACE heavy oil microreaction activity evaluation, those using the catalyst prepared by the method of the present invention have superior heavy oil conversion ability and coke selectivity compared to the comparative catalyst, and the total liquid yield. It can be seen that the rate and light oil yield are clearly higher than the comparative catalyst. Equation 1 shows the evaluation results of the catalyst B riser, and the catalyst of the present invention improves the total liquid yield by 0.97%, the light oil yield increases by 0.77%, and the gasoline properties substantially match those of the comparative catalyst G.

  As one of the main active components of the novel heavy oil catalyst described in the present invention, it is a high decomposition activity stable rare earth ultrastable Y type molecular sieve. In the rare earth modification preparation process, the molecular sieve uses NaY Pre-dispersing the molecular sieve reduces the degree of aggregation between the molecular sieve particles, brings more contact with the rare earth ions on the surface of the molecular sieve, reduces the resistance of the rare earth ions in the exchange process, and more molecular sieves The cage is exchanged into the cage and transitions to a sodalite cage in the subsequent steam baking process, thereby improving the structural stability and active stability of the molecular sieve. Rare earth ions are localized in the sodalite cage, there are no rare earth ions on the surface of the super cage and molecular sieve, the acid strength and density at that location are reduced, the probability of coke formation at the active site is reduced, and the heavy oil conversion of the catalyst He successfully solved the contradiction between Noh and coke selectivity.

Claims (21)

In the composition of the catalyst, 2 to 50% by weight of ultra-stable rare earth Y-type molecular sieve, 0.5 to 30% by weight of one or more other molecular sieves, 0.5 to 70% by weight of clay, 1.0% of high-temperature inorganic oxide A heavy oil catalytic cracking catalyst comprising ~ 65 wt% and rare earth oxide 0.01 to 12.5 wt%,
The ultra-stable rare earth Y-type molecular sieve is obtained by a preparation process including rare earth exchange and dispersion pre-exchange, containing 0.5 to 25% by weight of rare earth oxide, 1.2% by weight or less of sodium oxide, and crystallinity of 40 to 40%. 75%, lattice constant is 2.449nm ~ 2.472nm,
Rare earth exchange and dispersion pre-exchange are not limited sequentially but are performed continuously, and there is no firing process between them,
In the dispersion pre-exchange, the concentration of the molecular sieve slurry is adjusted to 80 to 400 g / L as the solid content, and the dispersion pre-exchange is performed by adding 0.2 to 7 wt% of the dispersant, and the exchange temperature is 0 to 100 ° C, replacement time is 0.1-1.5 hours,
The above dispersant in the dispersion pre-exchange is selected from sesbania powder, boric acid, urea, ethanol, polyacrylamide, acetic acid, oxalic acid, adipic acid, formic acid, hydrochloric acid, nitric acid, citric acid, salicylic acid, tartaric acid, benzoic acid, starch One or more types
A heavy oil catalytic cracking catalyst characterized in that no ammonium salt is used in rare earth exchange or dispersion pre-exchange.   The other molecular sieve is one or more selected from Y-type zeolite, L zeolite, ZSM-5 zeolite, b zeolite, aluminum phosphate zeolite, W zeolite, or modified zeolite described above. 2. The catalyst according to claim 1.   2. The catalyst according to claim 1, wherein the other molecular sieve is one or more of HY, USY, REY, REHY, REUSY, H-ZSM-5, and b zeolite.   2. The catalyst according to claim 1, wherein the clay is one or more selected from kaolin, halloysite, montmorillonite, sepiolite, and pearlite. _2. The catalyst according to claim 1, wherein the high temperature resistant inorganic oxide is one or more selected from Al ₂ O ₃ , SiO ₂ , SiO ₂ —Al ₂ O ₃ , and AlPO ₄ . During the catalyst production process,
(1) The molecular sieve slurry is not limited to the raw material, and the molecular sieve slurry is subjected to rare earth exchange and dispersion pre-exchange, and the molecular sieve slurry is further filtered, washed with water, and fired for the first time. Ultra-stable rare earth Y molecular sieves can be obtained by obtaining sodium Y molecular sieves, and reducing sodium by ammonium salt exchange in the “one-exchange-one-fired” rare earth sodium Y molecular sieves and firing the second time to obtain ultra-stable rare-earth Y-type molecular sieves. The sheave preparation process;
(2) Preparation of a heavy oil catalyst that can be obtained by mixing and homogenizing the above ultrastable rare earth Y-type molecular sieve with clay and high-temperature resistant inorganic oxide precursor, followed by spray molding, firing and washing with water. Process,
2. The method for producing a catalyst according to claim 1, comprising: Upon rare earth exchange, the RE ₂ O ₃ / Y zeolite mass ratio is 0.005-0.25, exchange temperature is 0-100 ° C., exchange pH value is 2.5-6.0, exchange time is 0.1-2 hours 7. The method for producing a catalyst according to claim 6, wherein   6. In the dispersion pre-exchange, the amount of dispersant added is 0.2 wt% to 7 wt%, the exchange temperature is 0 to 100 ° C., and the exchange time is 0.1 to 1.5 hours. The manufacturing method of the catalyst as described in 1 .. Upon rare earth exchange, its RE ₂ O ₃ / Y zeolite mass ratio is 0.01 ~ 0.20, exchange temperature is 60 ~ 95 ° C, exchange pH value is 3.5 ~ 5.5, exchange time is 0.3 ~ 1.5 hours In the dispersion pre-exchange, the amount of the dispersant added is 0.2 wt% to 5 wt%, the exchange temperature is 60 to 95 ° C., and the exchange time is 0.1 to 1.5 hours. 7. A method for producing the catalyst according to claim 6.   7. The method for producing a catalyst according to claim 6, wherein the molecular sieve slurry does not have to be washed and filtered between the rare earth exchange and the dispersion pre-exchange, and may be washed and filtered.   7. The method for producing a catalyst according to claim 6, wherein pot-type exchange, belt-type exchange and / or cake exchange are employed in the rare earth exchange or dispersion pre-exchange exchange process.   The rare earth compound solution is divided into a plurality of parts when performing rare earth exchange, pot type exchange, belt type exchange and / or cake exchange are performed, that is, a plurality of exchanges are performed. A method for producing a catalyst.   In the dispersion pre-exchange process, the dispersant is divided into a plurality of parts, pot-type exchange, belt-type exchange and / or cake exchange is performed, that is, a plurality of exchanges are performed. Production method.   7. The method for producing a catalyst according to claim 6, wherein when the rare earth exchange and the dispersion preliminary exchange are a plurality of exchanges, the two kinds of exchanges are alternately performed.   7. The method for producing a catalyst according to claim 6, wherein the calcining conditions for the first calcination of the molecular sieve are calcination at 350 ° C. to 700 ° C. and 0 to 100% steam for 0.3 to 3.5 hours.   7. The method for producing a catalyst according to claim 6, wherein the precursor of the high temperature resistant inorganic oxide is selected from silica alumina gel, silica sol, alumina sol, silica alumina composite sol, and pseudoboehmite.   13. The method for producing a catalyst according to claim 12, wherein the rare earth compound is a rare earth chloride, a rare earth nitrate, or a rare earth sulfate.   18. The method for producing a catalyst according to claim 17, wherein the rare earth described in the present invention is lanthanum enriched rare earth, cerium enriched rare earth, pure lanthanum, or pure cerium.   7. The method for producing a catalyst according to claim 6, wherein the calcination conditions in step (2) are that the sprayed microspheres are calcined at 200 ° C. to 700 ° C. and the time is 0.05 to 4 hours.   7. The method for producing a catalyst according to claim 6, wherein the calcination conditions in the step (2) are that the sprayed microspheres are calcined at 300 ° C. to 650 ° C. and the time is 0.1 to 3.5 hours.   7. The method for producing a catalyst according to claim 6, wherein water washing conditions in step (2) are: water / catalyst weight of 0.5 to 35, water washing temperature of 20 ° C. to 100 ° C., and time of 0.1 to 0.3 hours. .